Graphene membrane repair

ABSTRACT

Technologies described herein are generally related to systems and processes for repairing a graphene membrane on a support. A chamber may receive a layer of graphene on a support. The layer of graphene may include a hole. A first container including an initiator may be effective to apply an initiator through the hole to the support to functionalize the support and produce an initiator layer on the support. A second container including an activator may be effective to apply an activator through the hole to the initiator layer to activate the initiator layer. The application of the activator may further be effective to grow a polymer from the initiator layer. The growth of the polymer may be effective to produce a polymer plug in the hole and effective to repair at least a portion of the layer of graphene.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is related to the following application: PCTPatent Application No. PCT/US2012/______ (Attorney Docket NumberM-6300.061), entitled “REPAIRING GRAPHENE ON A POROUS SUPPORT” namingSeth Miller and Gary Duerksen as inventors, filed DATE, MONTH, YEAR,which is currently co-pending.

BACKGROUND

Unless otherwise indicated herein, the materials described in thissection are not prior art to the claims in this application and are notadmitted to be prior art by inclusion in this section.

Graphene is a material that generally may include a one atom thick layerof bonded carbon atoms. Graphene may be formed by growing carbon atomson top of another material such as copper. The copper may be insertedinto a quartz tube, heated, and annealed. A gas mixture of CH₄ and H₂may then be flowed into the tube and the copper may then be cooled withflowing H₂ to form graphene.

SUMMARY

In some examples, a method for repairing graphene is generallydescribed. Some example methods may include receiving, by a chamber, alayer of graphene on a support. The layer of graphene may include ahole. The method may include applying an initiator through the hole tothe support. The application of the initiator may be effective tofunctionalize the support and produce an initiator layer on the support.The method may further include applying an activator through the hole tothe initiator layer. The application of the activator may be effectiveto activate the initiator layer. The method may further include growinga polymer from the initiator layer using the activator. The growth ofthe polymer may be effective to produce a polymer plug in the hole.

In some examples, a system effective to repair a layer of grapheneincluding a hole is generally described. Some example systems mayinclude a chamber, a first container and/or a second container. Thechamber may be effective to receive the layer of graphene on a support.The first container may be in operative relationship with the chamber.The first container may include an initiator. The second container maybe in operative relationship with the chamber. The second container mayinclude an activator. The chamber may be configured effective to operatewith the first container to apply the initiator through the at least onehole to the support to functionalize the support and to produce aninitiator layer on the support. The chamber may further be configured tooperate with the second container to apply the activator through the atleast one hole to the initiator layer to activate the initiator layer.The chamber may be configured to operate with the second container togrow a polymer from the initiator layer using the activator to produce apolymer plug in the at least one hole.

In some examples a structure is generally described. Example structuresmay include a support. The structure may further include a layer ofgraphene on the support. The layer of graphene may include at least onehole region. The structure may further include a polymer plug in the atleast one hole region.

The foregoing summary is illustrative only and is not intended to be inany way limiting. In addition to the illustrative aspects, embodiments,and features described above, further aspects, embodiments, and featureswill become apparent by reference to the drawings and the followingdetailed description.

BRIEF DESCRIPTION OF THE FIGURES

The foregoing and other features of this disclosure will become morefully apparent from the following description and appended claims, takenin conjunction with the accompanying drawings. Understanding that thesedrawings depict only several embodiments in accordance with thedisclosure and are, therefore, not to be considered limiting of itsscope, the disclosure will be described with additional specificity anddetail through use of the accompanying drawings, in which:

FIG. 1 illustrates an example system that can be utilized to implementrepair of a graphene membrane on a support;

FIG. 2 illustrates an example system that can be utilized to implementrepair of a graphene membrane on a support;

FIG. 3 illustrates an example system that can be utilized to implementrepair of a graphene membrane on a support;

FIG. 4 illustrates an example system that can be utilized to implementrepair of a graphene membrane on a support;

FIG. 5 depicts a flow diagram for an example process for implementingrepair of a graphene membrane on a support;

FIG. 6 illustrates a computer program product that can be utilized toimplement repair of a graphene membrane on a support; and

FIG. 7 is a block diagram illustrating an example computing device thatis arranged to implement repair of a graphene membrane on a support;

-   -   all arranged according to at least some embodiments described        herein.

DETAILED DESCRIPTION

In the following detailed description, reference is made to theaccompanying drawings, which form a part hereof. In the drawings,similar symbols typically identify similar components, unless contextdictates otherwise. The illustrative embodiments described in thedetailed description, drawings, and claims are not meant to be limiting.Other embodiments may be utilized, and other changes may be made,without departing from the spirit or scope of the subject matterpresented herein. It will be readily understood that the aspects of thepresent disclosure, as generally described herein, and illustrated inthe Figures, can be arranged, substituted, combined, separated, anddesigned in a wide variety of different configurations, all of which areexplicitly contemplated herein.

This disclosure is generally drawn, inter alia, to systems, methods,materials and apparatus related to repairing a graphene membrane on asupport.

Briefly stated, technologies are generally described related to systemsand processes for repairing a graphene membrane on a support. A chambermay receive a layer of graphene on a support. The layer of graphene mayinclude a hole. A first container including an initiator may beeffective to apply an initiator through the hole to the support tofunctionalize the support and produce an initiator layer on the support.A second container including an activator may be effective to apply anactivator through the hole to the initiator layer to activate theinitiator layer. The application of the activator may further beeffective to grow a polymer from the initiator layer. The growth of thepolymer may be effective to produce a polymer plug in the hole andeffective to repair at least a portion of the layer of graphene.

It will be understood that any compound, material or substance which isexpressly or implicitly disclosed in the specification and/or recited ina claim as belonging to a group or structurally, compositionally and/orfunctionally related compounds, materials or substances, includesindividual representatives of the group and all combinations thereof.

FIG. 1 illustrates an example system that can be utilized to implementrepair of a graphene membrane on a support arranged in accordance withat least some embodiments described herein. An example graphene membranerepair system 100 may include one or more of a first container 102, asecond container 106, a support 52, a graphene membrane or graphenelayer 54 and/or a chamber 72 all configured in operative relationshipwith respect to one another. At least some of elements of graphenemembrane repair system 100 may be arranged in communication with aprocessor 154 through a communication link 156. In some examples,processor 154 may be adapted in communication with a memory 158 that mayinclude instructions 160 stored therein. Processor 154 may beconfigured, such as by instructions 160, to control at least some of theoperations/actions/functions described below.

As discussed in more detail below, graphene membrane 54 may includedesired pores 50 and undesired holes 56 or defects. Desired pores 50 maybe formed through patterning to create molecule sized holes. Desiredpores 50 may be, for example, about 1 Å to about 1 nm in length ordiameter. In an example, desired pores 50 may be generally unaffected byapplication of a graphene membrane repair process discussed herein.Undesired holes 56 may be between about 1 nm and about 5 nm in length ordiameter. First container 102 may be configured to operate with chamber72 to apply an initiator material 104 on support 52. Initiator material104 may be less reactive to graphene membrane 54 and more reactive tosupport 52 where holes 56 are present. Second container may beconfigured to operate with chamber 72 to apply a material 108 toactivate initiator material 104 resulting in localized polymerizationaround undesired holes 56. Activation of initiator material 104 maygenerate polymer plugs 58. Polymer plugs 58 may effectively close orsubstantially plug undesired holes 56.

FIG. 2 illustrates an example system that can be utilized to implementrepair of a graphene membrane on a support arranged in accordance withat least some embodiments described herein. FIG. 2 is substantiallysimilar to system 100, with additional details. Those components in FIG.2 that are labeled identically to components of FIG. 1 will not bedescribed again for the purposes of clarity.

System 100 may include a container 114 arranged in operativerelationship with chamber 72. Container 114 may include a material 116and a port 118. Support 52 may be treated, such as with an etchingprocess, to generate a cutout region 132 near undesired holes 56. Forexample, processor 154 may control the actuation of port 118 to open orclose and selectively allow material 116 to be applied through membrane54 and on to support 52 through undesired holes 56. Material 108 mayinclude iron chloride such as a solution including about 0.01 g/ml toabout 0.1 g/ml of iron chloride in water. Material 116 may be applied tosupport 52 for a time interval of about 2 minutes to about 10 minutes.Cutout region 132 may allow for polymer plug 58 to substantially anchorto both a bottom and a top side of membrane 54 thereby improvingadhesion.

FIG. 3 illustrates an example system that can be utilized to implementrepair of a graphene membrane on a support arranged in accordance withat least some embodiments described herein. FIG. 3 is substantiallysimilar to system 100, with additional details. Those components in FIG.3 that are labeled identically to components of FIGS. 1 and 2 will notbe described again for the purposes of clarity.

Support 52 may be made of a material effective to support graphenemembrane 54. For example, support 52 may be made of copper, nickel,silica, alumina, a polymer, etc. Initiator material 104 may be effectiveto functionalize support 52 so that a polymer may be grown on support 52at locations where holes 56 are present. In locations where graphene orpores 50 are present, initiator 104 may have difficulty functionalizingsupport 52. Initiator material 104 may be a material effective toinitiate a polymerization process on support 52. Initiator 104 may beselected to functionalize based on a material in substrate 52.

In an example, initiator material 104 may include a brominated silanolor a brominated thiol. Such an initiator may form a monolayer on support52 and may refrain from reacting with graphene membrane 56. In anexample, initiator material 104 may be formed by adding one part byvolume brominated silanol 120 to 10 parts by volume methanol 122 intocontainer 102 and stirred by a stirring device 128. Stirring device 128may be controlled by processor 154. Stirring device 128 may stirbrominated silanol 120 and methanol 122 for a time interval of about 1minute to about 10 minutes. Thereafter, 89 parts by volume of de-ionizedwater 124 may be added to container 102 to create a mixture. The mixturemay be stirred by stirring device 128 at a temperature in a range ofabout 30 degrees Celsius to about 50 degrees Celsius for a time intervalin a range of about 45 minutes to about 75 minutes. Heat may be appliedto container 102 by a heater 126. Thereafter, the mixture may be cooledto a temperature in a range of about 18 degrees Celsius to about 24degrees Celsius to produce initiator material 104. Initiator material104 may be applied to support 52 with membrane 54 such as by processor154 controlling port 110. Initiator material 104 may attach to support102 through holes 56 to form initiator layer 130.

Graphene membrane 54 may then be washed with methanol. For example,processor 154 may control port 110 to open and apply methanol 122 tomembrane 54. Methanol 122 may wash off portions of initiator material104 remaining on membrane 54. Membrane 54 and support 52 may then beheated to a temperature in a range of about 120 degrees Celsius to about170 degrees Celsius by heater 126.

FIG. 4 illustrates an example system that can be utilized to implementrepair of a graphene membrane on a support arranged in accordance withat least some embodiments described herein. FIG. 4 is substantiallysimilar to system 100, with additional details. Those components in FIG.4 that are labeled identically to components of FIG. 1-3 will not bedescribed again for the purposes of clarity.

Initiator layer 130 may be activated by material 108 such as with apolymerization process. The activation may form polymer plugs 58. Forexample, polymerization may occur in regions with holes 56 of a diameterlarger than a molecular size of monomers in initiator 104 In an example,polymer plug 56 may grow to a thickness and diameter of about 10 nm toabout 1 μm. Polymer plug 56 may have a hemispherical shape on a top ofmembrane 54. Polymer plug 56 may also have a hemispherical shape on abottom of membrane 54 when cutout regions 132 are formed.

For example an atom-transfer-radical polymerization process (ATRP) maybe used to grow plug 58. In other examples, a ring opening metatheses oranionic polymerization may be used. In an example, activation material108 may be formed by combining styrene, toluene, CuCl, CuBr₂, and/orbipyridine—all of which may be in one or more of containers 134, 136 or138. For example, about 4.2 g (40 mmol) of styrene, about 4.0 g toluene,about 19.8 mg (0.20 mmol) of CuCl, about 4.9 mg (0.020 mmol) of CuBr₂,and about 68.6 mg (0.440 mmol) of bipyridine may be combined incontainer 106 to form a mixture. The mixture may be heated to atemperature of about 35 degrees Celsius to about 50 degrees Celsius inan atmosphere lacking oxygen such as less than about 0.1% oxygen. Aheater 126 may be used to control a temperature in chamber 72. A pump142 may be used to control a pressure in chamber 72.

Activation material 108 may be applied to membrane 54 and initiatorlayer 130. Initiator layer 130 and activation material 108 may be heatedto a temperature in a range of about 30 degrees Celsius to about 50degrees Celsius in a vacuum for a time interval in a range of about 5minutes to about 15 minutes. Activation material 108 may activateinitiator 56 to form polymer plug 58. After forming plug 58, membrane 54may be washed with methanol, such as from one of containers 134, 136, or138 and then dried using heat from heater 126.

Material 108 may include a species that may be polymerized by a radicalprocess such as vinyls, styryls, acrylates, acrylamides, etc. A styrenemonomer may be used, as discussed above, and a resulting polymer mayhave relatively strong durability and adhesion to membrane 54. Shownbelow is an example of the chemistry which may occur where an acrylate,such as MMA (Methyl methacrylate), is used as a monomer.

Among other potential benefits, a system arranged in accordance with thepresent disclosure may facilitate use of graphene membranes producedwith relatively high defect counts, and perhaps made using lessexpensive manufacturing processes. These produced membranes may be usedwithout sacrificing graphene's relatively higher permeability/lowmembrane resistance or reducing the graphene's low gas transportselectivity. Such higher defect count membranes may be repaired byplugging undesired holes. Such undesired holes may otherwise degrade themembrane's ability to sieve molecules based on size. Undesired holes maybe plugged while a remainder of a membrane may still be unobstructed andused.

A graphene membrane repaired as discussed herein may be transferred toanother surface. Produced polymer plugs may be robust to handle a dry orwet etching process. The etching process may remove the support andreplace the support with a porous support. In a dry etching process, thedescribed plug may maintain good adhesion to the graphene membrane. In awet etching process, a solvent may be used and the described plug mayavoid being degraded by this solvent. In an example, a polar monomersuch as poly(hydroxyethylacrylate) may be used in the etching process.

FIG. 5 depicts a flow diagram for an example process 200 forimplementing repair of a graphene membrane on a support in accordancewith at least some embodiments described herein. The process in FIG. 5could be implemented using, for example, system 100 discussed above. Anexample process may include one or more operations, actions, orfunctions as illustrated by one or more of blocks S2, S4, S6 and/or S8.Although illustrated as discrete blocks, various blocks may be dividedinto additional blocks, combined into fewer blocks, or eliminated,depending on the desired implementation.

Process 200 may begin at block S2, “Receive, by a chamber, a layer ofgraphene on a support, wherein the layer of graphene includes a hole.”At block S2, a chamber may be configured effective to receive a layer ofgraphene on a support. The support may be made of, for example, copper,nickel, silica, alumina, a polymer, etc.

Processing may continue from block S2 to block S4, “Apply an initiatorthrough the hole to the support, the application of the initiator may beeffective to functionalize the support and produce an initiator layer onthe support.” In block S4, the chamber may be configured effective tooperate with a first container to apply an initiator through the hole tothe support. For example, a processor may selectively control (e.g.,actuate into an open or closed position) a port that is positionedbetween the first container and the chamber to apply the initiator fromthe first container to the chamber. The initiator may include, forexample, a brominated silanol or a brominated thiol.

In some examples, before the application of the initiator of block S4, acutout region may be formed in the support to receive the initiator. Forexample, iron chloride may be applied proximate to a cutout region onthe support effective to form the cutout region in the support. Afterapplication of the initiator, the layer of graphene may be washed, suchas with methanol, and dried.

Processing may continue from block S4 to block S6, “Apply an activatorthrough the hole to the initiator layer, the application of theactivator may be effective to activate the initiator layer.” At blockS6, the chamber may be configured effective to operate with a secondcontainer to apply an activator through the hole to the initiator layerto activate the initiator layer. For example, a processor mayselectively control a port that is positioned between the firstcontainer and the chamber to apply the initiator from the firstcontainer to the chamber. The activator may include one or more of avinyl, styryl, acrylate, and/or acrylamide.

Processing may continue from block S6 to block S8, “Grow a polymer fromthe initiator layer using the activator, the growth of the polymer maybe effective to produce a polymer plug in the hole and effective torepair at least a portion of the layer of graphene.” At block S6, theapplication of the activator to the initiator layer may be effective togrow a polymer from the initiator layer. The growth of the polymer maybe effective to produce the polymer plug in the hole. In an example,growing the polymer may include one or more of an atom-transfer-radicalpolymerization, a ring opening metatheses polymerization and/or ananionic polymerization.

FIG. 6 illustrates a computer program product that can be utilized toimplement repair of a graphene membrane on a support in accordance withat least some embodiments described herein. Program product 300 mayinclude a signal bearing medium 302. Signal bearing medium 302 mayinclude one or more instructions 304 that, when executed by, forexample, a processor, may provide the functionality described above withrespect to FIGS. 1-5. Thus, for example, referring to system 100,processor 154 may undertake one or more of the blocks shown in FIG. 6 inresponse to instructions 304 conveyed to the system 100 by medium 302.

In some implementations, signal bearing medium 302 may encompass acomputer-readable medium 306, such as, but not limited to, a hard diskdrive, a Compact Disc (CD), a Digital Video Disk (DVD), a digital tape,memory, etc. In some implementations, signal bearing medium 302 mayencompass a recordable medium 308, such as, but not limited to, memory,read/write (R/W) CDs, R/W DVDs, etc. In some implementations, signalbearing medium 302 may encompass a communications medium 310, such as,but not limited to, a digital and/or an analog communication medium(e.g., a fiber optic cable, a waveguide, a wired communications link, awireless communication link, etc.). Thus, for example, program product300 may be conveyed to one or more modules of the system 100 by an RFsignal bearing medium 302, where the signal bearing medium 302 isconveyed by a wireless communications medium 310 (e.g., a wirelesscommunications medium conforming with the IEEE 802.11 standard).

FIG. 7 is a block diagram illustrating an example computing device thatis arranged to implement repair of a graphene membrane on a supportaccording to at least some embodiments described herein. In a very basicconfiguration 402, computing device 400 typically includes one or moreprocessors 404 and a system memory 406. A memory bus 408 may be used forcommunicating between processor 404 and system memory 406.

Depending on the desired configuration, processor 404 may be of any typeincluding but not limited to a microprocessor (μP), a microcontroller(μC), a digital signal processor (DSP), or any combination thereof.Processor 404 may include one more levels of caching, such as a levelone cache 410 and a level two cache 412, a processor core 414, andregisters 416. An example processor core 414 may include an arithmeticlogic unit (ALU), a floating point unit (FPU), a digital signalprocessing core (DSP Core), or any combination thereof. An examplememory controller 418 may also be used with processor 404, or in someimplementations memory controller 418 may be an internal part ofprocessor 404.

Depending on the desired configuration, system memory 406 may be of anytype including but not limited to volatile memory (such as RAM),non-volatile memory (such as ROM, flash memory, etc.) or any combinationthereof. System memory 406 may include an operating system 420, one ormore applications 422, and program data 424. Application 422 may includea graphene repair algorithm 426 that is arranged to perform the variousfunctions/actions/operations as described herein including at leastthose described with respect to system 100 of FIGS. 1-6. Program data424 may include graphene repair data 428 that may be useful forimplementing repair of a graphene membrane on a support as is describedherein. In some embodiments, application 422 may be arranged to operatewith program data 424 on operating system 420 such that repair of agraphene membrane on a support may be provided. This described basicconfiguration 402 is illustrated in FIG. 7 by those components withinthe inner dashed line.

Computing device 400 may have additional features or functionality, andadditional interfaces to facilitate communications between basicconfiguration 402 and any required devices and interfaces. For example,a bus/interface controller 430 may be used to facilitate communicationsbetween basic configuration 402 and one or more data storage devices 432via a storage interface bus 434. Data storage devices 432 may beremovable storage devices 436, non-removable storage devices 438, or acombination thereof. Examples of removable storage and non-removablestorage devices include magnetic disk devices such as flexible diskdrives and hard-disk drives (HDD), optical disk drives such as compactdisk (CD) drives or digital versatile disk (DVD) drives, solid statedrives (SSD), and tape drives to name a few. Example computer storagemedia may include volatile and nonvolatile, removable and non-removablemedia implemented in any method or technology for storage ofinformation, such as computer readable instructions, data structures,program modules, or other data.

System memory 406, removable storage devices 436 and non-removablestorage devices 438 are examples of computer storage media. Computerstorage media includes, but is not limited to, RAM, ROM, EEPROM, flashmemory or other memory technology, CD-ROM, digital versatile disks (DVD)or other optical storage, magnetic cassettes, magnetic tape, magneticdisk storage or other magnetic storage devices, or any other mediumwhich may be used to store the desired information and which may beaccessed by computing device 400. Any such computer storage media may bepart of computing device 400.

Computing device 400 may also include an interface bus 440 forfacilitating communication from various interface devices (e.g., outputdevices 442, peripheral interfaces 444, and communication devices 446)to basic configuration 402 via bus/interface controller 430. Exampleoutput devices 442 include a graphics processing unit 448 and an audioprocessing unit 450, which may be configured to communicate to variousexternal devices such as a display or speakers via one or more A/V ports452. Example peripheral interfaces 444 include a serial interfacecontroller 454 or a parallel interface controller 456, which may beconfigured to communicate with external devices such as input devices(e.g., keyboard, mouse, pen, voice input device, touch input device,etc.) or other peripheral devices (e.g., printer, scanner, etc.) via oneor more I/O ports 458. An example communication device 446 includes anetwork controller 460, which may be arranged to facilitatecommunications with one or more other computing devices 462 over anetwork communication link via one or more communication ports 464.

The network communication link may be one example of a communicationmedia. Communication media may typically be embodied by computerreadable instructions, data structures, program modules, or other datain a modulated data signal, such as a carrier wave or other transportmechanism, and may include any information delivery media. A “modulateddata signal” may be a signal that has one or more of its characteristicsset or changed in such a manner as to encode information in the signal.By way of example, and not limitation, communication media may includewired media such as a wired network or direct-wired connection, andwireless media such as acoustic, radio frequency (RF), microwave,infrared (IR) and other wireless media. The term computer readable mediaas used herein may include both storage media and communication media.

Computing device 400 may be implemented as a portion of a small-formfactor portable (or mobile) electronic device such as a cell phone, apersonal data assistant (PDA), a personal media player device, awireless web-watch device, a personal headset device, an applicationspecific device, or a hybrid device that include any of the abovefunctions. Computing device 400 may also be implemented as a personalcomputer including both laptop computer and non-laptop computerconfigurations.

The present disclosure is not to be limited in terms of the particularembodiments described in this application, which are intended asillustrations of various aspects. Many modifications and variations canbe made without departing from its spirit and scope, as will be apparentto those skilled in the art. Functionally equivalent methods andapparatuses within the scope of the disclosure, in addition to thoseenumerated herein, will be apparent to those skilled in the art from theforegoing descriptions. Such modifications and variations are intendedto fall within the scope of the appended claims. The present disclosureis to be limited only by the terms of the appended claims, along withthe full scope of equivalents to which such claims are entitled. It isto be understood that this disclosure is not limited to particularmethods, reagents, compounds compositions or biological systems, whichcan, of course, vary. It is also to be understood that the terminologyused herein is for the purpose of describing particular embodimentsonly, and is not intended to be limiting.

With respect to the use of substantially any plural and/or singularterms herein, those having skill in the art can translate from theplural to the singular and/or from the singular to the plural as isappropriate to the context and/or application. The varioussingular/plural permutations may be expressly set forth herein for sakeof clarity.

It will be understood by those within the art that, in general, termsused herein, and especially in the appended claims (e.g., bodies of theappended claims) are generally intended as “open” terms (e.g., the term“including” should be interpreted as “including but not limited to,” theterm “having” should be interpreted as “having at least,” the term“includes” should be interpreted as “includes but is not limited to,”etc.). It will be further understood by those within the art that if aspecific number of an introduced claim recitation is intended, such anintent will be explicitly recited in the claim, and in the absence ofsuch recitation no such intent is present. For example, as an aid tounderstanding, the following appended claims may contain usage of theintroductory phrases “at least one” and “one or more” to introduce claimrecitations. However, the use of such phrases should not be construed toimply that the introduction of a claim recitation by the indefinitearticles “a” or “an” limits any particular claim containing suchintroduced claim recitation to embodiments containing only one suchrecitation, even when the same claim includes the introductory phrases“one or more” or “at least one” and indefinite articles such as “a” or“an” (e.g., “a” and/or “an” should be interpreted to mean “at least one”or “one or more”); the same holds true for the use of definite articlesused to introduce claim recitations. In addition, even if a specificnumber of an introduced claim recitation is explicitly recited, thoseskilled in the art will recognize that such recitation should beinterpreted to mean at least the recited number (e.g., the barerecitation of “two recitations,” without other modifiers, means at leasttwo recitations, or two or more recitations). Furthermore, in thoseinstances where a convention analogous to “at least one of A, B, and C,etc.” is used, in general such a construction is intended in the senseone having skill in the art would understand the convention (e.g., “asystem having at least one of A, B, and C” would include but not belimited to systems that have A alone, B alone, C alone, A and Btogether, A and C together, B and C together, and/or A, B, and Ctogether, etc.). In those instances where a convention analogous to “atleast one of A, B, or C, etc.” is used, in general such a constructionis intended in the sense one having skill in the art would understandthe convention (e.g., “a system having at least one of A, B, or C” wouldinclude but not be limited to systems that have A alone, B alone, Calone, A and B together, A and C together, B and C together, and/or A,B, and C together, etc.). It will be further understood by those withinthe art that virtually any disjunctive word and/or phrase presenting twoor more alternative terms, whether in the description, claims, ordrawings, should be understood to contemplate the possibilities ofincluding one of the terms, either of the terms, or both terms. Forexample, the phrase “A or B” will be understood to include thepossibilities of “A” or “B” or “A and B.”

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and allpurposes, such as in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range can be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein canbe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as “up to,” “at least,” “greater than,” “less than,” and the likeinclude the number recited and refer to ranges which can be subsequentlybroken down into subranges as discussed above. Finally, as will beunderstood by one skilled in the art, a range includes each individualmember. Thus, for example, a group having 1-3 cells refers to groupshaving 1, 2, or 3 cells. Similarly, a group having 1-5 cells refers togroups having 1, 2, 3, 4, or 5 cells, and so forth.

While various aspects and embodiments have been disclosed herein, otheraspects and embodiments will be apparent to those skilled in the art.The various aspects and embodiments disclosed herein are for purposes ofillustration and are not intended to be limiting, with the true scopeand spirit being indicated by the following claims.

What is claimed is:
 1. A system to repair a layer of graphene includinga hole, the system comprising: a chamber to receive the layer ofgraphene on a support; a first container in operative relationship withthe chamber, wherein the first container includes an initiator; and asecond container in operative relationship with the chamber, wherein thesecond container includes an activator; and wherein the chamber isconfigured to operate with the first container to apply the initiatorthrough the hole to the support to functionalize the support and toproduce an initiator layer on the support; operate with the secondcontainer to apply the activator through the hole to the initiator layerto activate the initiator layer; and operate with the second containerto grow a polymer from the initiator layer by use of the activator toproduce a polymer plug in the hole.
 2. The system of claim 1, whereinthe first and the second containers are different.
 3. The system ofclaim 1, wherein the initiator includes a brominated silanol or abrominated thiol.
 4. The system of claim 1, further comprising: a thirdcontainer in operative relationship with the chamber; and wherein thechamber is configured to operate with the third container to apply amaterial to a region in the support effective to form a cutout region.5. The system of claim 1, wherein the support comprises one or more ofcopper, nickel, silica, alumina, a polymer, etc.
 6. The system of claim1, wherein the activator comprises one or more of styrene, toluene,copper chloride, copper bromide, and/or bipyridine.
 7. The system ofclaim 1, wherein the activator comprises one or more of a vinyl, styryl,acrylate, and/or acrylamide.
 8. A structure comprising: a support; alayer of graphene on the support, the layer of graphene including poresand at least one hole region; and a polymer plug grown from the supportand in the at least one hole region of the layer of graphene.
 9. Thestructure of claim 8, wherein the polymer plug extends above an uppersurface of the layer of graphene and below a lower surface of the layerof graphene and into the support.
 10. The structure of claim 8, whereinthe polymer plug comprises one or more of a vinyl, styryl, acrylate,and/or acrylamide.